JPH10101809A - Organic peroxide-containing master batch and rubber composition - Google Patents
Organic peroxide-containing master batch and rubber compositionInfo
- Publication number
- JPH10101809A JPH10101809A JP27524596A JP27524596A JPH10101809A JP H10101809 A JPH10101809 A JP H10101809A JP 27524596 A JP27524596 A JP 27524596A JP 27524596 A JP27524596 A JP 27524596A JP H10101809 A JPH10101809 A JP H10101809A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer rubber
- organic peroxide
- rubber
- saturated copolymer
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は有機過酸化物含有マ
スターバッチに関し、詳しくはニトリル基含有高飽和共
重合ゴムとエチレン系飽和型共重合ゴムとの混合物に有
機過酸化物を多量含有させた有機過酸化物含有マスター
バッチに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic peroxide-containing masterbatch, and more particularly, to a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber containing a large amount of an organic peroxide. The present invention relates to a master batch containing an organic peroxide.
【０００２】[0002]
【従来の技術】加硫ゴム製品は、通常、原料ゴムに硫黄
及び加硫促進剤あるいは有機過酸化物等の加硫系及び補
強剤や充填剤等の各種配合剤を添加し、混合混練してコ
ンパウンド（組成物）を作製し、得られたコンパウンド
を用いて成形、加硫を行って製造される。2. Description of the Related Art Vulcanized rubber products are usually prepared by adding a vulcanizing system such as sulfur and a vulcanization accelerator or an organic peroxide and various compounding agents such as a reinforcing agent and a filler to a raw rubber and mixing and kneading. To produce a compound (composition), and then molding and vulcanizing using the obtained compound.
【０００３】その際、加硫促進剤等の粉末状の配合剤
は、秤量を容易にするためや混練中の飛散を防止するた
めにペレット状にして使用される場合がほとんどであ
る。しかしながら、混練中の剪断力でペレット状態は破
壊され、その際、一部は飛散し、量的に不足を生じるこ
とがしばしばある。又、有機過酸化物等の混練時に溶融
して液体状となるものは、混合機中で原料ゴムをスリッ
プさせ、これらを原料ゴム中に均一に分散させることが
困難となるばかりでなく、混練に長時間を要してしま
う。[0003] At that time, powdered compounding agents such as vulcanization accelerators are often used in the form of pellets in order to facilitate weighing and to prevent scattering during kneading. However, the pellet state is destroyed by the shearing force during kneading, and at that time, a part is scattered, and the shortage often occurs. In addition, when a material such as an organic peroxide is melted at the time of kneading to become a liquid, not only is it difficult to uniformly disperse the raw rubber in the raw rubber by slipping the raw rubber in the mixer, but also kneading. Takes a long time.
【０００４】上記のような問題を解決するために、予
め、多量の加硫促進剤や有機過酸化物等の配合剤と基材
ゴムとを混練して配合剤のマスターバッチを製造し、こ
のマスターバッチを配合剤が所定の量となるように原料
ゴムに添加することが一般的に行われている。例えば、
基材ゴムとしてニトリル基含有高飽和共重合ゴム（例え
ば、アクリロニトリル−ブタジエン共重合ゴムの水素化
物：Ｈ−ＮＢＲ）を用いた有機過酸化物マスターバッチ
を原料ゴムであるＨ−ＮＢＲに添加する例が特開平７−
１６５９９０号公報に記載されている。In order to solve the above problems, a large amount of a compounding agent such as a vulcanization accelerator or an organic peroxide and a base rubber are kneaded in advance to produce a master batch of the compounding agent. It is common practice to add a masterbatch to raw rubber so that the compounding agent has a predetermined amount. For example,
Example in which an organic peroxide masterbatch using a nitrile group-containing highly saturated copolymer rubber (for example, hydride of acrylonitrile-butadiene copolymer rubber: H-NBR) as a base rubber is added to H-NBR as a raw rubber. Is the Japanese
No. 165990.
【０００５】[0005]
【発明が解決しようとする課題】近年、Ｈ−ＮＢＲは比
較的高価なゴムであるために、エチレン−プロピレン系
共重合ゴムと混合することによりコスト低減を図ること
が試みられている。しかし、Ｈ−ＮＢＲとエチレン−プ
ロピレン系共重合ゴムとは相溶性が低いことに加えて、
いずれも有機過酸化物との親和性が低く、これらのゴム
の混合物と有機過酸化物とを効率よく混練することは困
難であった。In recent years, since H-NBR is a relatively expensive rubber, attempts have been made to reduce the cost by mixing it with an ethylene-propylene copolymer rubber. However, in addition to low compatibility between H-NBR and ethylene-propylene copolymer rubber,
In each case, the affinity for the organic peroxide was low, and it was difficult to efficiently knead a mixture of these rubbers with the organic peroxide.
【０００６】本発明はこのような事情に鑑みてなされた
ものであり、本発明の目的は、コストを低減し、ニトリ
ル基含有高飽和共重合ゴムの架橋製品の品質を一定水準
に維持した架橋ゴム製品の製造を可能とする有機過酸化
物含有マスターバッチを提供することにある。The present invention has been made in view of such circumstances, and it is an object of the present invention to reduce the cost and maintain the quality of a crosslinked product of a nitrile group-containing highly saturated copolymer rubber at a constant level. An object of the present invention is to provide an organic peroxide-containing master batch that enables production of rubber products.
【０００７】そこで、本発明者は上記の目的を達成すべ
く鋭意検討した結果、基材ゴムとしてニトリル基含有高
飽和共重合ゴムとエチレン系飽和型共重合ゴムとの混合
物を使用し、これに多量の有機過酸化物を添加してなる
有機過酸化物マスターバッチは、これを用いたニトリル
基含有高飽和共重合ゴムとエチレン系飽和型共重合ゴム
との混合物の架橋物性を低下させずにコスト削減が可能
であることを見いだし、この知見に基づき本発明を完成
するに至った。Accordingly, the present inventors have conducted intensive studies to achieve the above object, and as a result, have used a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber as a base rubber. An organic peroxide masterbatch obtained by adding a large amount of organic peroxide can be used without reducing the cross-linking properties of a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber. The inventors have found that cost reduction is possible, and have completed the present invention based on this finding.
【０００８】[0008]
【課題を解決するための手段】かくして本発明によれ
ば、ニトリル基含有高飽和共重合ゴム及びエチレン系飽
和型共重合ゴムとの混合物１００重量部当り、無機補強
剤及び／又は無機充填剤を３０〜３００重量部及び有機
過酸化物を４０〜１５０重量部含有することを特徴とす
る有機過酸化物含有マスターバッチが提供される。Thus, according to the present invention, an inorganic reinforcing agent and / or an inorganic filler is used per 100 parts by weight of a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber. An organic peroxide-containing masterbatch is provided, comprising 30 to 300 parts by weight and 40 to 150 parts by weight of an organic peroxide.
【０００９】[0009]
【発明の実施の形態】次に発明の好ましい実施の形態を
挙げて本発明をさらに詳細に説明する。本発明の特徴
は、有機過酸化物マスターバッチの基材ゴムとしてニト
リル基含有高飽和共重合ゴムとエチレン系飽和型共重合
ゴムとの混合物を使用することである。以下に各原料成
分について説明する。Next, the present invention will be described in more detail with reference to preferred embodiments of the present invention. A feature of the present invention is that a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber is used as a base rubber of an organic peroxide master batch. Hereinafter, each raw material component will be described.
【００１０】本発明で使用されるニトリル基含有高飽和
共重合ゴムは、アクリロニトリル、メタクリロニトリル
等のニトリル基含有不飽和化合物と１，３−ブタジエ
ン、２−メチル−１，３−ブタジエン、１，３−ペンタ
ジエン、２−クロロ−１，３−ブタジエン等の共役ジエ
ン系単量体の少なくとも一種との共重合体、（メタ）ア
クリル酸、マレイン酸、フマル酸、イタコン酸等の不飽
和カルボン酸；メチル（メタ）アクリレート、エチル
（メタ）アクリレート、ブチル（メタ）アクリレート、
２−エチルヘキシル（メタ）アクリレート、ラウリル
（メタ）アクリレート、グリシジル（メタ）アクリレー
ト、２−ヒドロキシエチル（メタ）アクリレート等の
（メタ）アクリル酸エステル；（メタ）アクリルアミ
ド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブト
キシメチル（メタ）アクリルアミド等の（メタ）アクリ
ル酸アミド及びその誘導体等のニトリル基含有不飽和化
合物及び共役ジエン系単量体と共重合可能な単量体の少
なくとも一種を共重合体中に０．１〜１５重量％程度さ
らに共重合させた共重合ゴム等の共役ジエン単量体単位
の二重結合を、通常の水素化触媒を用いて水素化したも
のが挙げられる。なかでも、アクリロニトリル−ブタジ
エン共重合ゴムを水素化したものが好ましい。ニトリル
基含有高飽和共重合ゴム中の不飽和ニトリル化合物の含
有量は、通常１０〜６０重量％、好ましくは２０〜５０
重量％、ヨウ素価は通常６０以下、好ましくは３０以
下、ムーニー粘度（ＭＬ1+4 ，１００℃）は通常２０〜
１５０、好ましくは６０〜９０の範囲である。[0010] The nitrile group-containing highly saturated copolymer rubber used in the present invention comprises a nitrile group-containing unsaturated compound such as acrylonitrile and methacrylonitrile and 1,3-butadiene, 2-methyl-1,3-butadiene, Copolymers with at least one conjugated diene monomer such as 1,3-pentadiene, 2-chloro-1,3-butadiene, and unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid Acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
(Meth) acrylic esters such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, At least one of a nitrile group-containing unsaturated compound such as (meth) acrylamide and its derivative such as N-butoxymethyl (meth) acrylamide and a monomer copolymerizable with a conjugated diene monomer is contained in the copolymer. And a double bond of a conjugated diene monomer unit such as a copolymer rubber further copolymerized by about 0.1 to 15% by weight is hydrogenated using a usual hydrogenation catalyst. Above all, those obtained by hydrogenating acrylonitrile-butadiene copolymer rubber are preferable. The content of the unsaturated nitrile compound in the nitrile group-containing highly saturated copolymer rubber is usually 10 to 60% by weight, preferably 20 to 50% by weight.
Wt%, iodine value is usually 60 or less, preferably 30 or less, and Mooney viscosity (ML 1 + 4 , 100 ° C.) is usually 20 to
150, preferably in the range of 60 to 90.
【００１１】本発明で使用れさるエチレン系飽和型共重
合ゴムは、エチレンとα−オレフィンとの共重合体また
はエチレンとα−オレフィンと非共役ジエンとの共重合
体であって、実質的に飽和型の共重合ゴムである。その
代表例は、エチレン−プロピレン共重合ゴム、エチレン
−プロピレン−非共役ジエン三元共重合ゴム、エチレン
−プロピレン−１−ブテン−非共役ジエン共重合ゴム、
エチレン−１−ブテン−非共役ジエン三元共重合ゴム等
のエチレンと炭素数が３〜１４のα−オレフィンを主成
分とする結晶化度が２０％以下、好ましくは１０％以下
の低結晶性又は非晶性のエラストマーまたはそれらの混
合物である。なかでも好ましいのはエチレン−プロピレ
ン−非共役ジエン三元共重合ゴムである。非共役ジエン
としては、ジシクロペンタジエン、１，４−ヘキサジエ
ン、シクロオクタジエン、メチレンノルボルネン、５−
エチリデン−２−ノルボルネン等が用いられ、ジシクロ
ペンタジエンまたは５−エチリデン−２−ノルボルネン
を使用する三元共重合ゴムが好ましい。The ethylene-based saturated copolymer rubber used in the present invention is a copolymer of ethylene and an α-olefin or a copolymer of ethylene, an α-olefin and a non-conjugated diene. It is a saturated copolymer rubber. Representative examples thereof are ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, ethylene-propylene-1-butene-non-conjugated diene copolymer rubber,
Low crystallinity having a crystallinity of 20% or less, preferably 10% or less mainly composed of ethylene and an α-olefin having 3 to 14 carbon atoms, such as ethylene-1-butene-non-conjugated diene terpolymer rubber. Or an amorphous elastomer or a mixture thereof. Of these, ethylene-propylene-non-conjugated diene terpolymer rubber is preferred. As the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, 5-
Ethylidene-2-norbornene and the like are used, and a terpolymer rubber using dicyclopentadiene or 5-ethylidene-2-norbornene is preferable.
【００１２】このようなエチレン系飽和型共重合ゴムの
ムーニー粘度（ＭＬ1+4 ，１００℃）は、通常、１０〜
１８０、好ましくは４０〜１４０であり、そのヨウ素不
飽和度は好ましくは２０以下である。エチレン系飽和型
共重合ゴム中のエチレン単位／とα−オレフィン単位は
５０／５０〜９０／１０（モル比）、好ましくは６０／
４０〜８４／１６（モル比）である。また、上記の三元
共重合ゴムにおける（エチレン＋α−オレフィン）単位
／非共役ジエン単位は、通常、９８／２〜９０／１０
（モル比）、好ましくは９７／３〜９４／６（モル比）
である。The Mooney viscosity (ML 1 + 4 , 100 ° C.) of such an ethylene-based saturated copolymer rubber is usually 10 to 10.
180, preferably 40 to 140, and the degree of iodine unsaturation is preferably 20 or less. The ethylene unit / and the α-olefin unit in the ethylene-based saturated copolymer rubber are 50/50 to 90/10 (molar ratio), preferably 60/50.
40 to 84/16 (molar ratio). The (ethylene + α-olefin) unit / non-conjugated diene unit in the above terpolymer rubber is usually from 98/2 to 90/10.
(Molar ratio), preferably 97/3 to 94/6 (molar ratio)
It is.
【００１３】上記のニトリル基含有高飽和共重合ゴムと
エチレン系飽和型共重合ゴムの混合割合は、特に限定さ
れないが、エチレン系飽和型共重合ゴムの割合が多過ぎ
ると本発明の有機過酸化物含有マスターバッチを原料ゴ
ムであるニトリル基含有高飽和共重合ゴムまたはニトリ
ル基含有高飽和共重合ゴムとエチレン系飽和型共重合ゴ
ムとの混合物に添加して得られれる架橋ゴム製品のこれ
らの原料ゴムの本来有する耐油性が損なわれ、少な過ぎ
るとコスト削減が達成されない。好ましい混合割合は、
ニトリル基含有高飽和共重合ゴム／エチレン系飽和型共
重合ゴムが９５〜２０／５〜８０（重量比）、さらに好
ましくは７０〜５０／３０〜５０（重量比）の範囲であ
る。The mixing ratio of the nitrile group-containing highly saturated copolymer rubber and the ethylene-based saturated copolymer rubber is not particularly limited. However, if the proportion of the ethylene-based saturated copolymer rubber is too large, the organic peroxide of the present invention may be used. Of a crosslinked rubber product obtained by adding a material-containing master batch to a raw rubber, a nitrile group-containing highly saturated copolymer rubber or a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber. The original oil resistance of the raw rubber is impaired, and if it is too small, cost reduction cannot be achieved. The preferred mixing ratio is
The ratio of the nitrile group-containing highly saturated copolymer rubber / ethylene-based saturated copolymer rubber is in the range of 95 to 20/5 to 80 (weight ratio), more preferably 70 to 50/30 to 50 (weight ratio).
【００１４】本発明で使用される有機過酸化物は、特に
限定されないが、室温で固体のものがマスターバッチを
製造する上で扱い易く好ましい。例えば、ジクミルパー
オキサイド、ｔ−ブチルクミルパーオキサイド、１，３
−及び１，４−ビス（ｔ−ブチルパーオキシイソプロピ
ル）ベンゼン、１，１−ジ−ｔ−ブチルパーオキシ−
３，３−トリメチルシクロヘキサン、４，４−ビス−
（ｔ−ブチル−パーオキシ）−ｎ−ブチルバレレート、
２，５−ジメチル−２，５−ジ−ｔ−ブチルパーオキシ
ヘキサン、２，５−ジメチル−２，５−ジ−ｔ−ブチル
パーオキシヘキシン−３、１，１−ジ−ｔ−ブチルパー
オキシ−３，５，５−トリメチルシクロヘキサン、ジ−
ｔ−ブチルパーオキサイド等が挙げられる。これらは一
種又は二種以上混合して使用することができる。The organic peroxide used in the present invention is not particularly limited, but a solid at room temperature is preferred because it is easy to handle in producing a masterbatch. For example, dicumyl peroxide, t-butylcumyl peroxide, 1,3
-And 1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-
3,3-trimethylcyclohexane, 4,4-bis-
(T-butyl-peroxy) -n-butylvalerate,
2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3,1,1-di-t-butyl Peroxy-3,5,5-trimethylcyclohexane, di-
t-butyl peroxide and the like. These can be used alone or in combination of two or more.
【００１５】本発明においては、有機過酸化物マスター
バッチを製造するうえで無機補強剤及び／又は無機充填
剤を使用することが不可欠である。これらを使用せずに
該マスターバッチを製造することは、有機過酸化物の融
解による基材ゴムの混合機中でのスリップを防止するこ
とができないために実質的に不可能である。In the present invention, it is essential to use an inorganic reinforcing agent and / or an inorganic filler in producing an organic peroxide masterbatch. It is virtually impossible to produce the masterbatch without using them, since it is not possible to prevent slippage of the base rubber in the mixer due to the melting of the organic peroxide.
【００１６】本発明で使用される無機補強剤としては、
例えば、カーボンブラック、シリカ、活性炭酸カルシウ
ム等が挙げられる。カーボンブラックとしては、ゴム分
野で使用されるカーボンブラックはいずれも使用するこ
とができる。例えば、チャンネルブラックとしては、Ｅ
ＰＣ、ＭＰＣ、ＨＰＣ等；ファーネスブラックとして
は、ＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＭＡＦ、ＦＥＦ、Ｆ
Ｆ、ＨＭＦ、ＧＰＦ、ＳＲＦ、ＡＰＦ、ＣＲＦ、ＣＦ、
ＳＣＦ、ＥＣＦ等；サーマルブラックとしては、ＭＴ、
ＦＴ、ＨＭＬ等が挙げられる。なかでもファーネスブラ
ックが好ましい。本発明のマスターバッチを用いた架橋
ゴム製品の引張り応力、引張り強さ等の物性を向上させ
る上から、ｐＨが７以上のカーボンブラックの使用が特
に好ましい。また、分散性の点から平均粒子径は４０μ
ｍ以上のものが好ましい。このようなカーボンブラック
としてはＳＲＦ、ＧＰＦ等が挙げられる。The inorganic reinforcing agent used in the present invention includes:
For example, carbon black, silica, activated calcium carbonate and the like can be mentioned. As the carbon black, any carbon black used in the rubber field can be used. For example, as the channel black, E
PC, MPC, HPC, etc .; Examples of furnace black include SAF, ISAF, HAF, MAF, FEF, F
F, HMF, GPF, SRF, APF, CRF, CF,
SCF, ECF, etc .; as thermal black, MT,
FT, HML and the like. Among them, furnace black is preferred. From the viewpoint of improving the physical properties such as the tensile stress and the tensile strength of the crosslinked rubber product using the masterbatch of the present invention, it is particularly preferable to use carbon black having a pH of 7 or more. Further, from the viewpoint of dispersibility, the average particle size is 40 μm.
m or more are preferable. Examples of such carbon black include SRF and GPF.
【００１７】シリカとしては、ゴム分野で使用されるシ
リカはいずれも使用することができる。例えば、湿式方
で製造される含水ケイ酸及び含水ケイ酸塩、乾式法で製
造される無水ケイ酸等が挙げられる。また、活性炭酸カ
ルシウムとしては、極微細炭酸カルシウムの表面を、例
えば、脂肪酸、樹脂酸、アニオン界面活性剤等で処理し
たものが挙げられる。As the silica, any silica used in the rubber field can be used. Examples thereof include hydrous silicic acid and hydrous silicate produced by a wet method, and silicic anhydride produced by a dry method. Examples of activated calcium carbonate include those obtained by treating the surface of ultrafine calcium carbonate with, for example, a fatty acid, a resin acid, an anionic surfactant, or the like.
【００１８】本発明で使用される無機充填剤としては、
例えば、沈降性及び重質炭酸カルシウム等の炭酸カルシ
ウム；炭酸マグネシウム、けい酸マグネシウム等；ハー
ドクレー、ソフトクレー、カオリンクレー等の含水けい
酸アルミニウムを主成分とするクレーまたは焼成クレ
ー；含水けい酸マグネシウムを主成分とするタルク；け
い藻土；アルミナホワイト、硫酸アルミニウム、硫酸バ
リウム、硫酸カルシウム、二硫化モリブデン、グラファ
イト等が挙げられる。これらの無機補強剤及び／又は無
機充填剤は一種または二種以上混合して使用することが
できるが、なかでもカーボンブラックの使用が好まし
い。The inorganic filler used in the present invention includes:
For example, calcium carbonate such as sedimentable and heavy calcium carbonate; magnesium carbonate, magnesium silicate; etc .; clay mainly containing hydrous aluminum silicate such as hard clay, soft clay, kaolin clay or calcined clay; hydrous magnesium silicate Diatomaceous earth; alumina white, aluminum sulfate, barium sulfate, calcium sulfate, molybdenum disulfide, graphite and the like. These inorganic reinforcing agents and / or inorganic fillers can be used alone or in admixture of two or more. Among them, the use of carbon black is preferred.
【００１９】本発明の有機過酸化物マスターバッチは、
基材ゴムとしての上記のニトリル基含有高飽和共重合ゴ
ムとエチレン系飽和型共重合ゴムとの混合物、無機補強
剤及び／又は無機充填剤及び有機過酸化物とを、ロー
ル、バンバリー、ニーダー、インターナルミキサー等の
通常の混合機を用いて混練することによって製造するこ
とができる。なかでもニーダーの使用が好ましい。混練
温度は特に制限されないが、通常４５〜８５℃の範囲で
あり、混練を有機過酸化物の分解温度以下の温度で行う
ことに注意すること以外は如何なる混練方法を用いても
よく、例えば、該基材ゴムと無機補強剤等と有機過酸化
物を同時に混練する方法、予めカーボンブラックと有機
過酸化物とを混合しておき、この混合物と該基材ゴムと
を混練する方法等が挙げられる。The organic peroxide masterbatch of the present invention comprises:
A mixture of the above-mentioned nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber as a base rubber, an inorganic reinforcing agent and / or an inorganic filler and an organic peroxide, roll, Banbury, kneader, It can be manufactured by kneading using a usual mixer such as an internal mixer. Of these, the use of a kneader is preferred. The kneading temperature is not particularly limited, but is usually in the range of 45 to 85 ° C., and any kneading method may be used except that the kneading is performed at a temperature equal to or lower than the decomposition temperature of the organic peroxide. A method of simultaneously kneading the base rubber, the inorganic reinforcing agent and the like and an organic peroxide, a method of previously mixing carbon black and an organic peroxide, and kneading the mixture with the base rubber and the like. Can be
【００２０】特に好ましい混練方法は、該基材ゴムと無
機補強剤及び／又は無機充填剤及び有機過酸化物とをニ
ーダー等の密閉型混合機中で混練する際に、有機過酸化
物のマスターバッチの製造にそれぞれ必要な量の無機補
強剤及び／又は無機充填剤と有機過酸化物とを少なくと
も２分割し、分割された無機補強剤及び／又は無機充填
剤及び有機過酸化物と該基材ゴムとを順次混練する方法
であり、大幅に混練時間を短縮することができる。A particularly preferred kneading method is to knead the base rubber with an inorganic reinforcing agent and / or an inorganic filler and an organic peroxide in a closed mixer such as a kneader. At least two portions of the inorganic reinforcing agent and / or the inorganic filler and the organic peroxide required for the production of the batch are divided into at least two parts, and the divided inorganic reinforcing agent and / or the inorganic filler and the organic peroxide and the base are separated. This is a method of sequentially kneading the material rubber and the kneading time can be greatly reduced.
【００２１】有機過酸化物のマスターバッチをより短時
間で製造するには、無機補強剤及び／又は無機充填剤及
び有機過酸化物の分割は、それぞれを２分割とすること
が好ましい。分割数を増やすと、混練時間が長くなり、
製造コストを増大させるので、該マスターバッチ中の有
機過酸化物の含有量が多くなり、有機過酸化物の溶融に
よって混練が困難となる等の特別な事情がある場合以外
は、出来るだけ分割数を少なくすることが望ましい。全
量のカーボンブラック及び有機過酸化物をそれぞれ２分
割する場合には、先ず、それぞれを５０重量％以上と５
０重量％未満の２分割物とし、いずれの分割においても
無機充填剤は有機過酸化物と同量もしくは無機充填剤が
有機過酸化物よりも少なくとも１０重量％多くなる量と
し、最初に５０重量％以上の各分割物と該基材ゴムとを
十分に混練し、次いで残りの各分割物を添加して十分に
混練することによって、短時間で均一な該マスターバッ
チが得られるので好ましい。さらに好ましくは、それぞ
れの全量の６０重量％以上９０重量％未満の分割物と１
０重量％以上４０重量％未満の分割物とに２分割するこ
とである。分割された無機充填剤と有機過酸化物は混練
に際しては、同時に該基材ゴムに添加しても、予め両者
を混合してから添加してもよい。生産性の観点から、予
め両者を混合して使用することが好ましい。In order to produce a master batch of an organic peroxide in a shorter time, the inorganic reinforcing agent and / or the inorganic filler and the organic peroxide are preferably divided into two parts. Increasing the number of divisions increases the kneading time,
Since the production cost is increased, the content of the organic peroxide in the masterbatch is increased, and unless there are special circumstances such as the fact that kneading becomes difficult due to the melting of the organic peroxide, the number of divisions is as small as possible. It is desirable to reduce When dividing the total amount of carbon black and the organic peroxide into two parts, first, each of the two parts is 50% by weight or more and 5 parts by weight.
Less than 0% by weight, divided into two parts, the inorganic filler in each of the divisions being the same amount as the organic peroxide or the amount of the inorganic filler being at least 10% by weight larger than the organic peroxide. % Or more and the base rubber are sufficiently kneaded, and then the remaining divided materials are added and kneaded sufficiently, so that a uniform master batch can be obtained in a short time. More preferably, 60% by weight or more and less than 90% by weight of the divided product and 1%
That is, it is divided into two parts, that is, 0 wt% or more and less than 40 wt%. At the time of kneading, the divided inorganic filler and the organic peroxide may be added to the base rubber at the same time, or may be added after mixing both in advance. From the viewpoint of productivity, it is preferable to use a mixture of the two in advance.
【００２２】上記の混練法を用いることによって、混練
中の有機過酸化物の溶融による該基材ゴムのスリップが
抑制され、混練温度を有機過酸化物の分解温度以下の温
度に制御することにより混練中の焼け（該基材ゴムの架
橋の進行）も防止され、短時間で該基材ゴムに無機補強
剤及び／又は無機充填剤及び有機過酸化物が均一に混練
された有機過酸化物のマスターバッチが製造される。By using the above kneading method, the slip of the base rubber due to the melting of the organic peroxide during kneading is suppressed, and the kneading temperature is controlled to a temperature lower than the decomposition temperature of the organic peroxide. An organic peroxide in which an inorganic reinforcing agent and / or an inorganic filler and an organic peroxide are uniformly kneaded with the base rubber in a short time is also prevented from burning during kneading (progress of crosslinking of the base rubber). Is manufactured.
【００２３】このようにして得られる本発明の有機過酸
化物含有マスターバッチは、ニトリル基含有高飽和共重
合ゴムとエチレン系飽和型共重合ゴムとの混合物１００
重量部当り、無機補強剤及び／又は無機充填剤を３０〜
３００重量部、有機過酸化物を４０〜１５０重量部含有
するものである。無機充填剤及び有機過酸化物の含有量
が上記の各上限量を超えると均一に混練された該マスタ
ーバッチを製造することが困難となり好ましくない。無
機補強剤及び／又は無機充填剤の含有量が３０重量部未
満では該マスターバッチ製造中の有機過酸化物の融解に
よる該共重合ゴムの混合機中でのスリップを抑制するこ
とが困難となる。また、有機過酸化物の含有量が４０重
量部未満では、該マスターバッチを原料ゴムに添加する
割合が多くなり過ぎて配合の自由度を小さくし、また架
橋ゴム製品の物性への影響も大きくなるので、マスター
バッチとするメリットはほとんどない。好ましい含有量
は、ニトリル基含有高飽和共重合ゴムとエチレン系飽和
型共重合ゴムとの混合物１００重量部当り、無機補強剤
及び／又は無機充填剤が８０〜２００重量部、有機過酸
化物が８０〜１２０重量部の範囲である。本発明の有機
過酸化物含有マスターバッチのなかでも、ＪＩＳ Ｋ−
６３００に従って測定した１２５℃の架橋反応における
スコーチタイム（Ｔ5 ）が５〜９分、キュアタイム（Ｔ
95）が１２〜１８分を示すものが好ましい。The organic peroxide-containing masterbatch of the present invention thus obtained is a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber.
30 parts by weight of an inorganic reinforcing agent and / or an inorganic filler per part by weight
It contains 300 parts by weight and 40 to 150 parts by weight of an organic peroxide. If the contents of the inorganic filler and the organic peroxide exceed the above-mentioned respective upper limits, it becomes difficult to produce the uniformly kneaded master batch, which is not preferable. When the content of the inorganic reinforcing agent and / or the inorganic filler is less than 30 parts by weight, it is difficult to suppress the slip of the copolymer rubber in the mixer due to the melting of the organic peroxide during the production of the master batch. . When the content of the organic peroxide is less than 40 parts by weight, the proportion of the masterbatch added to the raw rubber becomes too large to reduce the degree of freedom of blending, and also greatly affects the physical properties of the crosslinked rubber product. Therefore, there is almost no merit as a master batch. The preferred content is 80 to 200 parts by weight of an inorganic reinforcing agent and / or an inorganic filler, and 100 parts by weight of an organic peroxide per 100 parts by weight of a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber. It is in the range of 80 to 120 parts by weight. Among the organic peroxide-containing masterbatches of the present invention, JIS K-
The scorch time (T 5 ) in the crosslinking reaction at 125 ° C. measured according to 6300 is 5 to 9 minutes, and the cure time (T 5 )
95 ) shows 12 to 18 minutes.
【００２４】本発明の有機過酸化物含有マスターバッチ
は、各種原料ゴムの有機過酸化物供給源としてペレット
状あるいはシート状で使用される。該マスターバッチを
原料ゴムとしてニトリル基含有高飽和共重合ゴムまたは
ニトリル基含有高飽和共重合ゴムとエチレン系飽和型共
重合ゴムとの混合物に配合することによって良好な架橋
物性を示すゴム組成物が得られる。上記混合物において
は混合割合は特に限定されないが、ニトリル基含有高飽
和共重合ゴム／エチレン系飽和型共重合ゴムは、通常９
５／５〜２０／８０（重量比）、好ましくは７０／３０
〜５０／５０（重量比）である。The organic peroxide-containing masterbatch of the present invention is used in the form of pellets or sheets as an organic peroxide supply source for various raw rubbers. By blending the masterbatch as a raw rubber with a nitrile group-containing highly saturated copolymer rubber or a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber, a rubber composition exhibiting good cross-linking properties is obtained. can get. Although the mixing ratio of the above mixture is not particularly limited, the nitrile group-containing highly saturated copolymer rubber / ethylene-based saturated copolymer rubber usually has a mixing ratio of 9%.
5/5 to 20/80 (weight ratio), preferably 70/30
５０50/50 (weight ratio).
【００２５】上記の原料ゴムに対する本発明の有機過酸
化物含有マスターバッチの配合量は特に限定されない
が、通常、原料ゴム１００重量部に対して１〜５０重量
部、好ましくは１０〜２０重量部である。The amount of the organic peroxide-containing masterbatch of the present invention to the above-mentioned raw rubber is not particularly limited, but is usually 1 to 50 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the raw rubber. It is.
【００２６】[0026]
【実施例】以下に実施例及び比較例を挙げて本発明をさ
らに具体的に説明する。尚、以下においては部及び％
は、特に断りのない限り重量基準である。The present invention will be described more specifically below with reference to examples and comparative examples. In the following, parts and%
Are by weight unless otherwise specified.
【００２７】[0027]
実施例１及び２、比較例１及び２ ニトリル基含有高飽和共重合ゴム（日本ゼオン社製Ｚｅ
ｔｐｏｌ ２０２０Ｌ：アクリロニトリル含有量３６
％、ヨウ素価２８、ムーニー粘度（ＭＬ1+4 ，１００℃
＝５７．５）７５部、エチレン系飽和型共重合ゴムとし
てのＥＰＤＭ（エチレン−プロピレン−エチリデンノル
ボルネン三元共重合ゴム：三井石油化学社製ＥＰＴ−４
０７０、ヨウ素価２４）２５部、ＳＲＦカーボンブラッ
ク（東海カーボン社製シーストＳ：ｐＨ＝７．８）１３
３部及びジクミルパーオキサイド（ＤＣＰ）１００部を
ニーダーを用いて下記の方法で混練して有機過酸化物の
マスターバッチ（ＰＯ−ＭＢ１）を製造した。また、同
様にしてＦＥＦカーボンブラック（東海カーボン社製シ
ーストＳＯ：ｐＨ＝６．６）を用いて有機過酸化物のマ
スターバッチ（ＰＯ−ＭＢ２）を製造した。いずれの場
合も混練中はニーダーに冷却水を通し、混合物の温度を
ジクミルパーオキサイドの分解温度以下に保った。Examples 1 and 2, Comparative Examples 1 and 2 Nitrile group-containing highly saturated copolymer rubber (Zeon manufactured by Zeon Corporation)
tpol 2020L: acrylonitrile content 36
%, Iodine value 28, Mooney viscosity (ML 1 + 4 , 100 ° C
= 57.5) 75 parts, EPDM (ethylene-propylene-ethylidene norbornene terpolymer rubber as ethylene-based saturated copolymer rubber: EPT-4 manufactured by Mitsui Petrochemical Co., Ltd.)
070, iodine value 24) 25 parts, SRF carbon black (SEAIST S manufactured by Tokai Carbon Co., Ltd .: pH = 7.8) 13
3 parts and 100 parts of dicumyl peroxide (DCP) were kneaded using a kneader by the following method to produce a master batch (PO-MB1) of an organic peroxide. In addition, similarly, a master batch (PO-MB2) of an organic peroxide was produced using FEF carbon black (Seat SO manufactured by Tokai Carbon Co., Ltd., pH = 6.6). In each case, cooling water was passed through the kneader during kneading to maintain the temperature of the mixture at or below the decomposition temperature of dicumyl peroxide.
【００２８】（１）ニーダーに上記の基材ゴム３０ｋｇ
を投入し５分間素練りをする。 （２）予めカーボンブラック３０ｋｇ及びＤＣＰ２３ｋ
ｇを混合し、この混合物を投入し３．５分間混練する。 （３）予めカーボンブラック１０ｋｇ及びＤＣＰ７ｋｇ
を混合し、この混合物を投入し３分間混練し、混練物を
ニーダーより取り出す。 （４）ロールで均一に混練し、シート出しする。(1) Add 30 kg of the above base rubber to a kneader.
And masticate for 5 minutes. (2) 30kg of carbon black and 23k of DCP in advance
g, and the mixture is charged and kneaded for 3.5 minutes. (3) 10 kg of carbon black and 7 kg of DCP in advance
Are mixed, and this mixture is charged and kneaded for 3 minutes, and the kneaded material is taken out from the kneader. (4) The mixture is uniformly kneaded with a roll, and a sheet is taken out.
【００２９】上記のＰＯ−ＭＢ１及びＰＯ−ＭＢ２を用
い、高飽和ニトリル基含有共重合ゴム（日本ゼオン社製
Ｚｅｔｐｏｌ ２０１０Ｌ：アクリロニトリル含有量３
６％、ヨウ素価１１、ムーニー粘度（ＭＬ1+4 ，１００
℃＝５７．５）７５部と上記のＥＰＤＭ２５部との混合
物に表１に記載の配合処方で６インチロールを用いてコ
ンパウンドを作製した。また、上記の原料ゴムに直接Ｄ
ＣＰを配合したコンパウンドを作製した（比較例）。Using the above PO-MB1 and PO-MB2, a highly saturated nitrile group-containing copolymer rubber (Zetpol 2010L manufactured by Zeon Corporation: acrylonitrile content 3)
6%, iodine value 11, Mooney viscosity (ML 1 + 4,100
(° C. = 57.5) A compound was prepared from a mixture of 75 parts of the above EPDM and 25 parts of the above EPDM using a 6-inch roll with the formulation shown in Table 1. In addition, D
A compound containing CP was prepared (Comparative Example).
【００３０】これらのコンパウンドを作製するときに要
した混練時間、これらのコンパウンドの未架橋物性及び
１８０℃で８分プレス架橋して作製した２ｍｍ厚さのシ
ートを用いて架橋物性を測定した。結果を表１に示す。
試験法は下記の通りである。The kneading time required for preparing these compounds, the uncrosslinked physical properties of these compounds, and the crosslinked physical properties were measured using a 2 mm-thick sheet prepared by press-crosslinking at 180 ° C. for 8 minutes. Table 1 shows the results.
The test method is as follows.
【００３１】未架橋物性の測定方法 （１）コンパウンドムーニー粘度（ＭＬ1+4 ，１００
℃） ＪＩＳ Ｋ−６３００に従って１２５℃で測定。 （２）スコーチタイム（Ｔ5 ：分）及びキュアータイム
（Ｔ95：分） ＪＩＳ Ｋ−６３００に従って１２５℃で測定。 架橋物性の測定方法 ＪＩＳ Ｋ−６３０１に従って測定。Measurement Method of Uncrosslinked Physical Properties (1) Compound Mooney Viscosity (ML 1 + 4 , 100
C) Measured at 125 C according to JIS K-6300. (2) Scorch time (T 5 : minute) and cure time (T 95 : minute) Measured at 125 ° C. according to JIS K-6300. Method for measuring cross-linking properties Measured according to JIS K-6301.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】以上の本発明によれば、有機過酸化物を
ニトリル基含有高飽和共重合ゴムとエチレン系飽和型共
重合ゴムとの混合物に配合する際の混練時間が大幅に短
縮される。また、ニトリル基含有高飽和共重合ゴムとエ
チレン系飽和型共重合ゴムとの混合物に本発明の有機過
酸化物のマスターバッチを必要量添加して製造した架橋
ゴム製品は、有機過酸化物を上記の混合物に直接配合し
て製造した通常の架橋ゴム製品と比較して良好な架橋物
性を示す。According to the present invention, the kneading time when compounding an organic peroxide with a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber is greatly reduced. . In addition, a crosslinked rubber product produced by adding a required amount of the organic peroxide masterbatch of the present invention to a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber contains an organic peroxide. Good cross-linking properties are obtained as compared with ordinary cross-linked rubber products produced by directly compounding the above mixture.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 23/18 Ｃ０８Ｌ 23/18 33/18 33/18 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 23/18 C08L 23/18 33/18 33/18
Claims (4)
レン系飽和型共重合ゴムとの混合物１００重量部当り、
無機補強剤及び／又は無機充填剤を３０〜３００重量部
及び有機過酸化物を４０〜１５０重量部含有することを
特徴とする有機過酸化物含有マスターバッチ。1. Per 100 parts by weight of a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber,
An organic peroxide-containing masterbatch comprising 30 to 300 parts by weight of an inorganic reinforcing agent and / or an inorganic filler and 40 to 150 parts by weight of an organic peroxide.
重合ゴム／エチレン系飽和型共重合ゴムが９５〜２０／
５〜８０（重量比）である請求項１に記載の有機過酸化
物含有マスターバッチ。2. The mixture according to claim 1, wherein said nitrile group-containing highly saturated copolymer rubber / ethylene-based saturated copolymer rubber is 95-20 /
The organic peroxide-containing masterbatch according to claim 1, which has a weight ratio of 5 to 80.
ボンブラックである請求項１又は２に記載の有機過酸化
物含有マスターバッチ。3. The organic peroxide-containing masterbatch according to claim 1, wherein the inorganic reinforcing agent and / or the inorganic filler is carbon black.
レン系飽和型共重合ゴムとの混合物１００重量部当り、
請求項１に記載の有機過酸化物含有マスターバッチ１〜
５０重量部を配合してなるニトリル基含有高飽和共重合
ゴム組成物。4. Per 100 parts by weight of a mixture of a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber,
The organic peroxide-containing masterbatch 1 according to claim 1.
A nitrile group-containing highly saturated copolymer rubber composition containing 50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27524596A JP3617888B2 (en) | 1996-09-27 | 1996-09-27 | Method for producing organic peroxide-containing masterbatch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27524596A JP3617888B2 (en) | 1996-09-27 | 1996-09-27 | Method for producing organic peroxide-containing masterbatch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10101809A true JPH10101809A (en) | 1998-04-21 |
| JP3617888B2 JP3617888B2 (en) | 2005-02-09 |
Family
ID=17552727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27524596A Expired - Lifetime JP3617888B2 (en) | 1996-09-27 | 1996-09-27 | Method for producing organic peroxide-containing masterbatch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3617888B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212362A (en) * | 2001-01-23 | 2002-07-31 | Gomuno Inaki Kk | Ethylene-propylene copolymer rubber composition |
| JP2002275326A (en) * | 2001-03-19 | 2002-09-25 | Asahi Denka Kogyo Kk | Granular compounded additive for polyolefin and method of its manufacture |
| KR100888495B1 (en) | 2007-10-08 | 2009-03-12 | 평화오일씰공업주식회사 | Method of manufacturing rubber for oil seal |
-
1996
- 1996-09-27 JP JP27524596A patent/JP3617888B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212362A (en) * | 2001-01-23 | 2002-07-31 | Gomuno Inaki Kk | Ethylene-propylene copolymer rubber composition |
| JP2002275326A (en) * | 2001-03-19 | 2002-09-25 | Asahi Denka Kogyo Kk | Granular compounded additive for polyolefin and method of its manufacture |
| JP4662218B2 (en) * | 2001-03-19 | 2011-03-30 | 株式会社Ａｄｅｋａ | Granular composite additive for polyolefin and process for producing the same |
| KR100888495B1 (en) | 2007-10-08 | 2009-03-12 | 평화오일씰공업주식회사 | Method of manufacturing rubber for oil seal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3617888B2 (en) | 2005-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4687810A (en) | Making rubber blends of diene rubber & EPR or EPDM | |
| US5036132A (en) | Rubber blends | |
| CA1330843C (en) | Elastomeric composition having increased ozone resistance | |
| JP2006169523A (en) | Multi-stage manufacturing method of peroxide-curable hxnbr-polyamide thermoplastic resin vulcanizate | |
| JPH0611815B2 (en) | Curable composition and method for producing elastomer composition | |
| JP2006526694A (en) | Co-reagent for preparing thermoplastic elastomer blends of rubber and polyolefin | |
| JP2609369B2 (en) | Tire side surface composition | |
| WO1996032430A1 (en) | Precure retardation of free radical cured elastomers | |
| US3451962A (en) | Process for improved sulfur-vulcanization of mixtures of elastomers containing ethylene propylene terpolymers | |
| JP3617888B2 (en) | Method for producing organic peroxide-containing masterbatch | |
| JP3597956B2 (en) | Method for producing organic peroxide-containing masterbatch | |
| JP2000248096A (en) | Foamable rubber composition and foamed rubber | |
| US4604420A (en) | Vulcanizable polymer compositions with improved scorch | |
| JP3626563B2 (en) | Organic peroxide-containing masterbatch | |
| JP2000248116A (en) | Organic-peroxide-crosslinkable fiber-reinforced rubber composition and its production | |
| JPH0820693A (en) | Halogenated butyl rubber composition | |
| EP1292625B1 (en) | Cure promoters and methods for vulcanizing elastomers | |
| JP3597955B2 (en) | Manufacturing method of organic peroxide masterbatch | |
| JP3411076B2 (en) | Method for producing hydrogenated acrylonitrile-butadiene copolymer rubber product and organic peroxide masterbatch | |
| JPH0222332A (en) | Production of fiber-reinforced rubber composition | |
| EP2922910B1 (en) | Method of manufacturing an elastomeric product with a low hysteresis | |
| JPS61250042A (en) | Rubber composition with high wear resistance | |
| JPH0476063A (en) | Thermoplastic elastomer composition | |
| JP2798303B2 (en) | Method for producing thermoplastic elastomer composition and thermoplastic elastomer composition | |
| JPH02281054A (en) | Production of fiber reinforced rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040528 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040601 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040802 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040824 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041006 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041102 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041105 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081119 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081119 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091119 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091119 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101119 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111119 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111119 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121119 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121119 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 9 |
|
| EXPY | Cancellation because of completion of term |